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At least 253 records · Page 14

Predicting the tensile and compressive modulus of electrospun fiber mat‐reinforced hydrogels using the Halpin–Tsai equations

Abstract The reinforcement of mechanically‐weak hydrogels to yield composites with increased stiffness, strength, or toughness is a well‐established approach. In particular, introducing electrospun nanofibers into hydrogels is a common strategy for biomedical applications, as the resulting hierarchical structure mimics biology and allows for control over fiber diameter and alignment and tuning of mechanical properties. However, further study of the link between the constituent materials and the mechanical properties of the composite is uncommon. One potential model to understand the mechanical properties of fiber‐reinforced hydrogels involves the Halpin–Tsai equations, which relate the modulus values of the fibers and hydrogel matrix and the fiber volume fraction, to the modulus of the composite. To assess the application of this model to fiber‐reinforced hydrogels, predicted values were compared with experimental values from mechanical testing of a poly(ethylene glycol) (PEG) matrix reinforced with an electrospun polycaprolactone (PCL) fiber mat. Although the equations described these systems well in tension, providing a facile approach to identify a fiber volume fraction that will achieve a desired modulus, the Halpin–Tsai approach was less successful under compression. This study motivates additional investigation of the role of structural features of hydrogel composites in determining mechanical properties to enable design of materials for specific applications.

Polymer Science↗

Static and Fatigue Characterization of Large Composite T-Bolt Connections in Marine Hygrothermal Environments

Fiber-reinforced polymer composites have been highlighted as ideal candidates for structural applications in marine renewable energy devices, such as tidal turbines and wave energy converters. It is well understood that harsh marine environments can cause strength degradation of composite laminates, which has been extensively researched at the coupon scale; however, no research has investigated how this translates into larger-scale composite structures. This paper presents a subcomponent-scale study which investigates the effects of hygrothermal aging and subsequent static and fatigue characterization of thick composite T-bolt connections as part of a large, multilaboratory materials research effort. Of the glass-reinforced epoxy and vinylester-epoxy matrix composites tested, both showed measurable static strength degradation (4–36%) after being hygrothermally aged, even though the composite specimens were only partially saturated with water. Under tension–tension fatigue loading, the epoxy specimens performed very well in their dry states but exhibited significant degradation after hygrothermal aging. In comparison, the vinylester-epoxy specimens had much shorter fatigue lives in their dry states but exhibited no degradation after hygrothermal aging. Overall, this research demonstrates that hygrothermal aging can have significant effects on the ultimate strengths and fatigue lives of even partially saturated thick composite T-bolt connections, indicating that degradation of the outer plies on thick composite laminates can have pronounced effects on the whole structure. It discusses the challenges of building an understanding of the effects of harsh marine environments in large-scale composite structures.

16 TIDAL AND WAVE POWER↗

Topological structure enhanced nanostructure of high temperature polymer exhibiting more than ten times enhancement of dipolar response

Nanofillers in polymer composites will induce interface regions in the polymer with non-uniform nanostructures which can be approximated as multilayer shells surrounding nanofillers. This paper studies topological nanostructures in polymers that interface with one-dimensional (1-D) and zero-dimensional (0-D) nanofillers. This new class of dielectric polymer nanocomposites involves nanofillers at ultra-low volume loading (< 1 vol percent) that generate large dielectric enhancement. The results show that the dipolar response of polyetherimide, a high temperature dielectric polymer, is increased by more than ten times with ultra-low (0.75 vol %) loading of 1-D nanofillers. The results reveal that 1-D nanofillers induce cylindrical shell-topology in the polymer matrix which is more effective in enhancing the high dielectric constant interfacial region than the spherical shell-topology generated by 0-D fillers. Furthermore, the cylindrical shells generated by 1-D fillers provide much higher dielectric enhancement over a broader interfacial region in the polymer matrix, as compared to the spherical shells induced by 0-D nanofillers.

42 ENGINEERING↗

Medial packing and elastic asymmetry stabilize the double-gyroid in block copolymers

Triply-periodic networks are among the most complex and functionally valuable self-assembled morphologies, yet they form in nearly every class of biological and synthetic soft matter building blocks. In contrast to simpler assembly motifs – spheres, cylinders, layers – networks require molecules to occupy variable local environments, confounding attempts to understand their formation. Here, we examine the double-gyroid network phase by using a geometric formulation of the strong stretching theory of block copolymer melts, a prototypical soft self-assembly system. The theory establishes the direct link between molecular packing, assembly thermodynamics and the medial map, a generic measure of the geometric center of complex shapes. We show that “medial packing” is essential for stability of double-gyroid in strongly-segregated melts, reconciling a long-standing contradiction between infinite- and finite-segregation theories. Additionally, we find a previously unrecognized non-monotonic dependence of network stability on the relative entropic elastic stiffness of matrix-forming to tubular-network forming blocks. The composition window of stable double-gyroid widens for both large and small elastic asymmetry, contradicting intuitive notions that packing frustration is localized to the tubular domains. This study demonstrates the utility of optimized medial tessellations for understanding soft-molecular assembly and packing frustration via an approach that is readily generalizable far beyond gyroids in neat block copolymers.

36 MATERIALS SCIENCE↗

Melt compounding of spray-dried cellulose nanofibrils/polypropylene and their application in 3D printing

Abstract Micro- and nano-scale cellulosic fillers exhibit excellent dispersion and distribution within a thermoplastic matrix during the process of melt compounding or injection molding. In this study, spray-dried cellulose nanofiber (SDCNF) powders were manufactured using a pilot-scale rotating disk atomizer spray dryer. Bleached Kraft pulp (BKP), unbleached Kraft pulp (UKP), and old corrugated cardboard pulp (OCC) fibrillated at a fines level of 90% were used as feedstock materials for spray-drying. BKP-, UKP-, and OCC- SDCNFs were compounded with polypropylene using a twin screw co-rotating extruder. Maleic anhydride grafted polypropylene (MAPP) was used as a coupling agent in the composite formulations. The tensile, flexural, and impact properties of SDCNF-filled PP composites increased at 10 wt% SDCNF loading. The presence of SDCNFs in the PP matrix resulted in faster crystallization and a 12% reduction in the degree of crystallinity of the neat PP. The coefficient of thermal expansion (CTE) of neat PP was reduced by up to 31% attributable to the presence of the SDCNFs. Application of the SDCNF-reinforced PP composites in 3D printing reduced the shrinkage rate of the printed neat PP by 39%, and the printability of the PP was significantly improved with the addition of the SDCNFs.

Materials Science↗

PBI nanofiber mat-reinforced anion exchange membranes with covalently linked interfaces for use in water electrolysers

Anion exchange membranes (AEM) are key components in anion exchange membrane water electrolysers. Recently developed materials are less susceptible to the alkaline degradation of the polymer backbone and quaternary ammonium groups. A remaining challenge is the mechanical stability in contact with hot water and dimensional stability when the temperature of the feed solution changes. One solution is to reinforce membranes with a porous support. Since support materials like PEEK or PTFE have a different swelling behavior than the matrix and no strong interactions with the matrix, voids can form, and gas crossover increases. In this work, we approach this issue by pore filling polybenzimidazole nanofiber mats with the bromomethylated precursor of mTPN, an ultra-stable AEM material. During drying, a covalent interaction between support (PBI amine groups) and matrix (-CH 2 Br) is established. After quaternization, the optimized PBI/mTPN-50.120 composite membrane still shows a high conductivity of 62 mS cm –1 , but 37% reduced length swelling in comparison to the non-reinforced membrane. Tensile strength and Young's modulus increase 17% and 56% to 49 MPa and 680 MPa, respectively. In an electrolyser, a stable voltage of 1.98V at 0.25 A cm –2 was achieved, and no change in membrane resistance was observed over the test time of 200 h (50°C, 1 M KOH, catalysts based on Ni/Fe and Mo).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of DMP-30 catalyst concentration on the degradation and kinetics of bisphenol A epoxy thermosets cured with linear amine hardener

Epoxy thermosets are a crucial component in carbon-fiber composites, serving as the organic binding matrix. Catalysts are commonly used in prepolymer formulations to accelerate curing of the thermosets. However, the impact of catalysts on the thermal stability, degradation pathways, and kinetics of the final thermoset is poorly understood. Here, in this work, Product-Specific Kinetics (PSK) analysis was utilized with isoconversional kinetics to provide a first look into the degradation kinetics of major pyrolysis pathways in bisphenol A (BPA) epoxy resins and determine the impact of altering catalysis concentrations on these kinetic pathways. Results revealed new insights into previously identified degradation pathways, provided evidence of multiple degradation pathways for some products, and showed that use of excess catalyst results in polymer network alterations and reduced thermal stability of the thermosets.

Bisphenol A↗

Fiber Sorbents – A Versatile Platform for Sorption-Based Gas Separations

Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs. These processability limitations have been historically addressed through powder shaping methods aimed at the fabrication of structured sorbent contactors based on pellets, beads or monoliths, commonly obtained as extrudates. These structures overcome limitations such as elevated pressure drops commonly recorded across powder adsorption beds but often accrue thermal limitations arising from elevated particle density and aggregation, which ultimately cap their maximum separation performance. Furthermore, the harsh mechanical strain to which powder particles are subjected during contactor fabrication, in the form of extrusion/compression forces, can result in partial pore occlusion and framework degradation, further limiting their performance. Here, we present the development of porous fiber sorbents as an alternative sorbent contactor design capable of addressing sorbent processability limitations while enabling an array of performance-maximizing heat integration capabilities. This new sorbent form factor leverages pre-existing know-how from hollow fiber spinning to produce fiber-shaped sorbent contactors through the phase inversion of known polymers in a process known as dry-jet/wet quenching. The process of phase inversion allows microporous sorbent particles to be latched onto a macroporous polymer matrix under mild processing conditions, thus making it compatible with soft porous materials prone to amorphization under traditional pelletization conditions. Sorbent fibers can be created with different geometries through control of the spinning apparatus and process, offering the possibility to produce monolithic and hollow fibers alike, the latter of which can be integrated with thermalization fluid flows. In this Account, we summarize our progress in the field of fiber sorbents from both design and application standpoints. We further guide the reader through the evolution of this field from the early inceptive work on zeolite hollow fibers to recent developments on MOF fibers. We highlight the versatile nature of fiber sorbents, both from the composition, fabrication and structure points of view, and further demonstrate how fiber sorbents offer alternative paths in tackling new and challenging chemical separation challenges like direct air capture (DAC), with a final perspective on the future of the field.

36 MATERIALS SCIENCE↗

Testing Protocol Development for the Fracture Toughness of Parts Built with Big Area Additive Manufacturing

The mechanical testing of additively manufactured parts has largely relied on the existing standards developed for traditional manufacturing. While this approach leverages the investment made in current standards development, it inaccurately assumes that the mechanical response of additive manufacturing (AM) parts is identical to that of parts manufactured through traditional processes. When considering thermoplastic, material extrusion AM, the differences in response can be attributed to an AM part’s inherent inhomogeneity caused by porosity, interlayer zones, and surface texture. Additionally, the interlayer bonding of parts printed with large-scale AM is difficult to adequately assess, as much testing is performed such that stress is distributed across many layer interfaces; therefore, the lack of AM-specific standards to assess interlayer bonding is a significant research gap. To quantify interlayer bonding via fracture toughness, double cantilever beam (DCB) testing has been used for some AM materials, and DCB has been generally used for a variety of materials including metal, wood, and laminates. Mode I DCB testing was performed on thermoplastic matrix composites printed with Big Area Additive Manufacturing (BAAM). Of particular interest was the notch shape and deflection speed during testing. The results examine the differences when using two notch types and three deflection speeds. The testing method introduced by the following paper differentiates itself from the ones described in the standards used by modernizing the methodology. This was conducted with the introduction of Digital Image Correlation (DIC) to gather displacement and load data simultaneously without human intervention.

Polymer Science↗

Hygrothermal aging and recycling effects on mechanical and thermal properties of recyclable thermoplastic glass fiber composites

Abstract Glass fiber‐reinforced polymer composites are widely used in marine applications, including renewable energy devices and submarines, due to their strength‐to‐weight ratios and corrosion resistance. As sustainability becomes more important, recyclable thermoplastic composites are gaining attention in marine energy applications. These materials face harsh conditions such as high chloride water, UV radiation, pressurization, and thermal cycling, which can affect their durability and recyclability. This study examines the impact of hygrothermal aging on the recyclability of an Elium glass fiber (GF) composite. Samples were mechanically ground for recycling, and mechanical and thermal properties were compared between aged and unaged samples. After seawater aging, the tensile strength and modulus of the unaged composite dropped by 25% and 13% respectively, due to water ingress along the fiber‐matrix interface. The recycled composite showed reduced flexural strength as the long fiber composite was converted into short fibers during the process. Differential scanning calorimetry (DSC) revealed no change in glass transition temperature after aging. Weight loss (25%) was attributed to the thermal stability of the glass fibers. Dynamic mechanical analysis (DMA) showed that the storage modulus increased with aging, and fracture analysis confirmed a mixed mode of failure for aged composites. Highlights Hygrothermal aging lowers mechanical performance of Elium® GF composites. Failure mechanism tends to be matrix cracking and interface bonding. Glass transition temperature is not reduced by hygrothermal aging. Fractured composite was successfully recycled via thermoforming. Flexural strength of the recycled composite is lower.

17 WIND ENERGY↗

Direct ink writing of shear exfoliated two-dimensional nanomaterial- elastomeric multifunctional nanocomposite

Direct ink writing (DIW) of polymer nanocomposites with high loadings of two-dimensional (2D) nanofillers (graphene and hexagonal boron nitride (hBN)) is challenging because of potential clogging, use of hazardous solvents, and agglomeration. Here, in this work, a shear exfoliation and sieving method to prepare DIW ink with high loading of nanofillers produced from low-cost bulk layered materials such as graphite and bulk hBN powder for successful DIW printing without the use of any solvents, binders, or plasticizers. The single-step exfoliation technique resulted in a composite with substantial layer reduction along the c-axis, as confirmed by SEM, TEM, XRD, and Raman analysis. Incorporating exfoliated graphene (40 wt%) increased viscosity by ∼6 orders of magnitude due to enhanced particle–matrix interactions, leading to pronounced yield stress behavior and a yield stress of approximately 1598 Pa, which enabled excellent shape retention during extrusion. Using the DIW technique, porous structures such as desalination membranes, self-sensing bone scaffolds, thermal management coating, and serpentine strain sensors were fabricated. When tested in a direct contact membrane distillation setup, the fabricated membrane demonstrated a promising permeate flux of 21.85 Lm −2 h −1 and a salt rejection of 74.3 %. The fabricated serpentine sensor exhibited stable signal variations under cyclic tensile loading, with a working range of 0–200 % strain and a maximum gauge factor of 43,735. A cell culture test using the printed bone scaffold demonstrated promising cell attachment and proliferation. The DIW printed hBN nanocomposite exhibited reversible shape change under heat, demonstrating potential 4D printing capability and efficient thermal management when exposed to high heat or flame.

Desalination↗

Chitosan as a Canvas for Studies of Macromolecular Controls on CaCO 3 Biological Crystallization

A mechanistic understanding of how macromolecules, typically as an organic matrix, nucleate and grow crystals to produce functional biomineral structures remains elusive. Advances in structural biology indicate that polysaccharides (e.g., chitin) and negatively charged proteoglycans (due to carboxyl, sulfate, and phosphate groups) are ubiquitous in biocrystallization settings and play greater roles than currently recognized. This review highlights studies of CaCO 3 crystallization onto chitinous materials and demonstrates that a broader understanding of macromolecular controls on mineralization has not emerged. With recent advances in biopolymer chemistry, it is now possible to prepare chitosan-based hydrogels with tailored functional group compositions. By deploying these characterized compounds in hypothesis-based studies of nucleation rate, quantitative relationships between energy barrier to crystallization, macromolecule composition, and solvent structuring can be determined. Finally, this foundational knowledge will help researchers understand composition-structure-function controls on mineralization in living systems and tune the designs of new materials for advanced applications.

15 GEOTHERMAL ENERGY↗

Carbon Additive Manufacturing with a Near-Replica “Green-to-Brown” Transformation

Nanocomposites containing nanoscale materials offer exciting opportunities to encode nanoscale features into macroscale dimensions, which produces unprecedented impact in material design and application. However, conventional methods cannot process nanocomposites with a high particle loading, as well as nanocomposites with the ability to be tailored at multiple scales. A composite architected mesoscale process strategy that brings particle loading nanoscale materials combined with multiscale features including nanoscale manipulation, mesoscale architecture, and macroscale formation to create spatially programmed nanocomposites with high particle loading and multiscale tailorability is reported. The process features a low-shrinking (<10%) “green-to-brown” transformation, making a near-geometric replica of the 3D design to produce a “brown” part with full nanomaterials to allow further matrix infill. Here, this demonstration includes additively manufactured carbon nanocomposites containing carbon nanotubes (CNTs) and thermoset epoxy, leading to multiscale CNTs tailorability, performance improvement, and 3D complex geometry feasibility. The process can produce nanomaterial-assembled architectures with 3D geometry and multiscale features and can incorporate a wide range of matrix materials, such as polymers, metals, and ceramics, to fabricate nanocomposites for new device structures and applications.

36 MATERIALS SCIENCE↗

New sterically hindered polyvinylamine-containing membranes for CO 2 capture from flue gas

Amine-containing facilitated transport membranes can have both high permeability and selectivity due to the reversible reaction between CO 2 and amino groups for effective carbon capture from flue gas. In this study, we have developed an improved method for the synthesis of high-molecular-weight sterically hindered polyvinylamine (PVAm) as the new fixed-site carrier in thin-film composite membranes for CO 2 capture. Commercially available PVAm was N-monomethylated into poly-N-methyl-N-vinylamine (PVAm-CH 3 ) using the stepwise reductive amination with a highly polar fluorinated alcohol as the solvent to enhance the equilibrium shift to the formation of the imine intermediate. The method prevented over-alkylation, resulting in the increased yield of the target product. PVAm-CH 3 exhibited excellent CO 2 facilitation with a CO 2 permeability of 445.7 Barrer (1 Barrer = 3.349 x 10 –16 mol m m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 70.3, which are above the Robeson 2008 upper bound. The PVAm-CH 3 solution retained a sufficiently high viscosity after incorporating the aminoacid salt, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar), as the mobile carrier for the membrane coating on nanoporous polyethersulfone (PES) substrates without any penetration issues. The resultant thin-film composite PVAm-CH3/PZEA-Sar membrane with a thickness of approximately 170 nm exhibited a superior CO 2 performance of 1071 GPU (1 GPU = 3.349 x 10 –10 mol m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 183 at 57°C and a feed gas pressure of 111.64 kPa (1.5 psig). This PVAm-CH 3 /PZEA-Sar membrane surpassed the latest redefined 2019 CO 2 /N 2 upper bound and outperformed other polymer-based membranes. Density functional theory calculations also demonstrated that PVAm-CH 3 showed a stronger preference, relative to PVAm, toward the more efficient bicarbonate pathway. Thus, the steric hindrance effect of PVAm-CH 3 enhanced the solubility of CO 2 in the polymer matrix and resulted in the higher CO 2 permeance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A multifunctional technology platform for sorbent construction using polyacrylonitrile scaffolds

Polyacrylonitrile (PAN) is a synthetic polymer that shows high potential for use in a wide range of environmental remediation applications. PAN can be implemented in various ways within a batch or continuous process stream for use as a passive scaffold holding active gettering materials in place or where the PAN scaffold (e.g., beads, fiber mats, membranes) is functionalized with active chelating groups (e.g., amine, hydrazide, amidoximes, carboxyl). Application spaces covered in this review include remediation of heavy metals (e.g., Ag, As, Cd, Cr6+, Cu, Pb, Sb, and Se), high-dose fission products (e.g., 90Sr, 137Cs), radioiodine (i.e., 129I), noble gases (i.e., Xe, 85Kr), rare earths (e.g., Ce, Y), and actinides (e.g., Am, Pu, U). Methods for producing PAN composite sorbents are discussed. Options are also discussed for removing the PAN matrix following chemisorption of an active contaminant to minimize waste volumes requiring disposal.

polyacrylonitrile, composite sorbents, sulfides, a↗

How to Get the Best Gas Separation Membranes from State-of-the-Art Glassy Polymers

Herein we focus on fundamental polymer science factors in membrane-based gas separation to open another chapter on this important topic. Realistically thinking about nano and angstrom scale matrix attributes that are translatable into higher performance thin glassy polymer asymmetric membrane layers in practical large-scale devices is crucial. Such thinking should be guided by expertise in both polymer and membrane communities to advance the state of the art. Polymer structures, membrane morphologies and effects of operating conditions are discussed here, using specific examples to illustrate key issues. Rubbery polymers are not the focus of this discussion, since they lack diffusive discrimination for size-similar penetrants, which glassy polymers provide and make them the focus here. Four scalable subtopics guide necessary thinking: (i) plasticization; (ii) anti-plasticization†2; (iii) dual-mode transport involving saturation of unrelaxed free volume, and (iv) non-uniform free volume and stress profiles in thin skin glassy polymer asymmetric or composite membranes. Furthermore, using these subtopics in the context of macromolecular science we discuss issues needed to expand the state-of-the-art in gas separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunable PA6 Polymer System for Thermoplastic Reinforced Body Panels

Project Goal: Overall, a redesigned polyamide system will combine the ductility and processing of a PA6 matrix, the strength and modulus of CF, and the facile recyclability of esters. Approach: PEA can be synthesized under conventional, industrially relevant pathways. Material properties and processing will be analyzed and compared to commercial PA6 material. Results: Polycondensation, traditional for polyesters, was successful in synthesized a PEA. PEA exhibited fast crystallization and bimodal melting behavior suggesting beneficial crystallization kinetics. PEA exhibit reduced melting temperatures owed to the incorporation of ester units in the polymer structure.

42 ENGINEERING↗

Mechanically and Thermally Enhanced 3D-Printed Photocurable Polymer Nanocomposites Containing Functionalized Chitin Nanowhiskers by Stereolithography

Additive manufacturing, or simply 3D printing (3DP), where objects are built through layer-wise material deposition, has gained significant academic and industrial attention as a result of the development of advanced and functional materials requiring rapid, customized, and flexible solutions. In the context of green manufacturing, diversifying environmentally and economically sustainable material portfolios is an essential endeavor for the success of 3DP technology that uses widely available, highly valuable, and renewable materials. Here, we used stereolithography (SLA) for processing methacrylate-based photocurable resins containing crab shell-derived chitin nanowhiskers (CNWs), which are surface-functionalized by reactive acrylate groups. Results from full spectral, thermal, structural, and topological analyses corroborate not only the surface functionalization of CNWs but also indicate the presence of these photocurable CNW (pCNW) fillers in the 3D-printed nanocomposites. Owing to the strong interfacial bond induced by the physical and chemical crosslinking between the pCNW and methacrylate (MA) polymer matrix, the internally formulated nanocomposites displayed enhanced thermomechanical properties (e.g., storage modulus and glass transition temperature) compared to those of commercially available pure SLA resins. For instance, the inclusion of 0.5 wt % pCNW improved the tensile strength and stiffness to up to 78 and 71%, respectively, without compromising the toughness and ductility of the printed material. Accordingly, this result also evidences the compatibility between the filler and resin materials. Consequently, the formation of a crosslinked network in the nanocomposite structure results in a higher thermal stability and activation energy (i.e., up to ~79%) for all the hybrid materials than the pristine MA. Finally, the high-resolution SLA print features, dimensional accuracy, and enhanced mechanical performance of our microstructure-forming functionalized chitin-based nanocomposites make them promising materials for a wide range of robust and high-performance industrial applications.

36 MATERIALS SCIENCE↗